sabato 30 aprile 2022

THE PRIMORDIAL BROTH in 2022 (The first myth: origin, expectations and failures. Part one)

 

Post n. 3 update (first part)


But when did the 'primordial soup' (or prebiotic soup) theory begin?

Around 1870, in a letter to a friend, Darwin wrote: "If (and this is a big if) we could imagine that in a small hot pool, rich in ammonia, phosphoric salts, light, heat, electricity, etc., a protein compound was chemically formed, ready to go through even more complex changes [...]". But Darwin's official position was firm and clear: in the present state of knowledge it is not possible (ultra vires) to formulate a theory of the origin of life.

In 1924 A. I. Oparin, who at that time held the chair of Plant Biochemistry at Moscow University, translated this idea into a kind of scientific theory and published it in a book "Origine della vita" Ed.Bor. 1977: According to Oparin, on our planet carbon was bound to metals in the form of carbides. These, coming into contact with water vapour, reacted to form hydrocarbons and through subsequent reactions many other organic compounds. 



                                                              Ev-03.jpgAggregatimolec.Brodo priom.1
  

When the temperature at the earth's surface dropped below 100°C, water began to condense and all these compounds, contained in the atmosphere, were swept into a 'primitive boiling ocean' where they began to react to form larger and larger molecules. The subsequent aggregation of these macromolecules would give rise to gel particles, 'coacervates'. The organic coacervates would have absorbed and assimilated substances from the environment and then, as they divided, would have given rise to 'primitive organisms', some of which were capable of metabolising. The evolutionary process and natural selection would eventually give rise to all living organisms.

According to Mario Ageno (Biosifica 3, 1984), a pupil of Enrico Fermi and a co-worker of Edoardo Amaldi, an attentive and profound scholar of biophysics: "The fundamental idea is certainly very brilliant and has lost none of its interest even today. However, this must not make us forget that such a "theory" passes over in silence all the great problems, all the great challenges that the idea of an origin of life from inorganic matter by natural causes poses to our minds".

But even Haldane, while adding a brilliant idea, goes no further.

In 1929 J. B. S. Haldane, without knowing Oparin's ideas, published a short article on the origin of life. According to Haldane, the primitive atmosphere did not contain oxygen, but probably H2 (hydrogen), H2O (water), CO2 (carbon dioxide), and presumably also CH4 (methane) NH3 (ammonia). More complex molecules would have been formed in the atmosphere by solar radiation. These organic compounds, carried away by the rain, would have accumulated in the primitive ocean where they would have reacted to form complex molecules, giving rise to a 'dilute warm soup' where the first organisms would have originated.

The dilute warm soup was immediately translated into 'Primordial Broth'; the metaphor was born and the theory began.

 

miller2.gif Schema dell'esp.di Miller 1


  

Around 1950, an operational research programme began with H. Urey and S. Miller. In particular, using a gas mixture of H2 (hydrogen), H2O (water), CH4 (methane) NH3 (ammonia) similar to the atmospheres of Jupiter, Saturn and Uranus, with the addition of energy (electrical discharges), Miller succeeded in producing amino acids, which are components of proteins, and many other organic substances.

Haldane's theory of a primitive atmosphere devoid of O2 and the formation in the atmosphere of substances fundamental to the origin of life and their collection in a 'primordial soup' where life would have originated, thus seemed to be confirmed.

It was at this time that prebiological chemistry was born, with the aim of identifying, in addition to the amino acids already discovered, the formation of molecules fundamental to the origin of life and their synthesis in an environment similar to that of the earth at the time of the appearance of life. In the years that followed, a number of tests were carried out that confirmed the results of Miller's experiment. In addition, a number of researchers carried out 'Miller-like' experiments, varying both the composition of the gas mixture and the energy sources. All of this work confirmed that in prebiotic times, a large number of organic substances could be synthesised on our planet, often including amino acids.

At the same time, the same substances, particularly amino acids, were found in meteorites (carbonaceous chondrite) dating back to the time of the formation of our solar system. The discovery of amino acids in Miller's experiments and their presence in meteorites demonstrated, according to scientists, the ease with which these compounds could be synthesised. The discoveries aroused great enthusiasm among scientists and it seemed that the mystery of life would soon be unravelled.  But the major problems, passed over in silence by Oparin and Haldane in their theory of the prebiotic broth, proved insurmountable not only, as we shall see, from a chemical-physical point of view, but also from the point of view of contemporaneity and localisation. In fact, it is unthinkable that the processes we are going to list could have taken place at different times, because the substances fundamental to the origin of life would have decomposed in the meantime. Nor is it conceivable that they could have taken place in different places because in that case the fundamental substances would never have met.

But what are the big problems that the prebiotic broth theory passes over in silence?

For each of these problems, a few comments from authoritative scientists and, if any, the solutions proposed by the supporters of the primordial broth theory.

1) The molecules of amino acids, the components of proteins, exist in two forms, Destro and Levo, and one is the mirror image of the other. If you prepare amino acids in the laboratory, for example Alanine, what you get is 50% Alanine Destro and 50% Alanine Levo. These two molecular forms have the same chemical/physical properties and always travel together; their natural separation in a prebiotic broth or in the laboratory is not possible unless an asymmetric substance is present; but this would shift the problem to the origin of the new asymmetric substance. The amino acids discovered by Miller in his now famous experiment were also half right-handed and half left-handed, as were the amino acids found in meteorites. So in the prebiotic world the amino acids must have been half L and half D.

                                        Ala L                          Ala D

                   

The issue is that, the proteins of all living organisms are made up of Levo amino acids.

                                                                      Ala L


How did their separation come about and what happened to the Destro?

According to Dickerson (The Sciences; Gl albori della vita, 1984):"[...] it may be that, at some time, there was primitive life, or precursors to it, based on both D and L amino acids with a 50% probability and that, in the end, the L amino acids prevailed over the others".

Most scientists consider this last solution implausible. It is difficult enough to imagine the origin of a primitive life, to imagine two, one Destro and the other Levo, is really hard.

R. A. Hegstrom and D. K. Kondepudi, addressed the problem of asymmetry in an article in Le Scienze "La chiralità dell’universo" 1990. As the authors illustrate, chemical compounds originate through electromagnetic interactions of the atoms of which they are composed. During these processes parity is said to be conserved, i.e. if a compound is formed its mirror image has the same probability of forming.

The particles making up the atom, protons, neutrons and electrons, are held together by various forces. Two of these forces, the weak nuclear force and the electroweak force, do not maintain parity.

In the earth's crust of our planet there are elements whose atoms decay and emit radiation (radioactive decay). During radioactive decay, high-velocity electrons, β-rays (beta), are also emitted.  Without going into too much detail, the weak nuclear force is responsible for this decay, and since it does not maintain parity, more left-handed electrons are emitted than right-handed ones. When β-rays strike chiral molecules they decompose them, but being mostly left-handed they preferentially destroy a shape leaving an excess of its mirror image. It was therefore thought that the weak nuclear force was responsible for the asymmetry of life. It was found that the relative difference in decomposition rates is of the order of one part in 109, or one part in 1 000 000 000 (one billion).

The second force, the electroweak force, contributes to the formation of compounds.

Since even this force does not preserve parity, it has been calculated that during their formation, in prebiotic times, Levo amino acids must have been more abundant than dextro amino acids on the order of one in 1017, we are spared writing a 1 followed by 17 zeros.

Although these contributions are very small to determine molecular asymmetry, Kondepudi and a collaborator, Nelson, attempted to demonstrate theoretically that amplification processes can exist under particular conditions. He imagines a tank in which Dextrous and Left are competing and writes: 'And the tank should be large enough and sufficiently well mixed (the stirring should be about 10 square kilometres in area and several metres deep) to eliminate to a great extent the resulting effect of random fluctuations. If all these conditions were met, the weak nuclear force should be able to strongly influence the symmetry-breaking process over a period of 50000 to 100000 years". Kondepudi and Hegstrom conclude: "We have set out numerous models to demonstrate how chiral asymmetry may have developed in biomolecules. [...]. However, none of them has been able to indicate a particular group of prebiotic compounds with all the properties required by these models.

Robert M. Hazen took up the problem of molecular asymmetry in 2001 in an article in Le Scienze: 'Vita dale rocce'. As the title indicates, Hazen turns his attention to the mineral world and prefigures a unique model. That is, he imagines that concentration, selection and synthesis may have taken place within small air pockets of volcanic pumice or feldspathic rocks. For these events, the author does not consider deterministic events and instead states: 'Chance may have produced a combination of molecules that would eventually have deserved to be called "living"'.

Hazen then tackles the problem of molecular asymmetry by turning his attention to calcite crystals, limestones and marbles, because these crystals form pairs of mirror faces. As he explains, the calcite crystals were immersed in a solution containing a 50% Destro and Levo amino acid. After 24 hours, the crystal was extracted and washed and the solution analysed. The Levo faces of the calcite mainly selected amino acid L with an excess of 40% and vice versa. Hazen did not question the physical causes of this phenomenon and stated: "Strangely enough, the more terraced faces were the most selective. This fact led us to predict that the edges of the terraces might force the amino acids to line up in neat rows on their respective faces". Since left and right-handed crystal faces are equal in degree, he concludes: 'It was by pure chance that the molecule destined for success developed in a crystal face that preferred Left-handed amino acids to their Right-handed counterparts'.

Ultimately a unique but random pattern, i.e. a miracle.

2) There are only 20 amino acids in our proteins but, in Miller's experiments, about 60 different amino acids were found. How did this choice come about and why only 20 amino acids?

 The prevailing explanation is the obvious one: there were false starts that became extinct because they could not compete with the lines that survived.

3) Reactions between amino acids for protein synthesis all take place with the elimination of H2O. In an aqueous environment, i.e. in the primordial soup, this reaction is not only chemically impossible but proteins in water tend to break down into amino acids and this break down is accelerated by heat.

According to S. Fox, proteins would have formed near the volcanic cones at a temperature of 200°C and only later would they have been washed away by rain and collected in the broth, where they would have formed microspheres that were resistant to the destructive action of water. Alternatively, it was imagined that the primordial soup was actually a pool of water close to the ocean and subject to continuous evaporation. The problem has also been solved by imagining secondary reactions between amino acids with energy-rich compounds, but these steps greatly multiply the number of reactions. Hundreds of reactions would have been needed to obtain a polymer of 40 amino acids, and this seems scarcely credible.

Ultimately, the question is still open.

4) The primitive atmosphere certainly did not contain O2 (oxygen) and therefore the O3 (ozone) shield was absent. Ultraviolet rays, in greater quantities than today, reached the surface of the earth. In a primitive ocean, they reached a depth of 10 metres. Diffusion, thermal agitation and currents would sooner or later bring all organic substances into this band and they would be destroyed.


                                                      bocche idrotermali.jpg univeronline.it 

  

To solve this problem, it is imagined that the first organisms originated anchored to the bottom of shallow lagoons not much deeper than 10 metres. For some researchers, the problem does not exist, as life would have originated on the ocean floor near the mouths of the hydrothermal vents.

Now, it is obvious to anyone that all the hypotheses made to fill these gaps are in fact ad hoc modifications, often in contradiction with each other and without any possibility of experimental verification.

In "The roots of biology" 1986 Mario Ageno writes: "We can therefore say that at the beginning of the 1980s research into the origin of life entered a crisis".

But in 1983 a major discovery revitalised the prebiotic soup theory. Cech and Altmann discover 'Ribozymes'.

Nucleic acids (DNA and RNA) and proteins (enzymes) are fundamental macromolecules for living organisms, and there is no doubt that in a primitive organism they could not be lacking. However, while nucleic acids contain the genetic information for the assembly of proteins, the latter are necessary for the assembly of nucleic acids. Nucleic acids and proteins are interdependent, i.e. one needs the other. This is what is known in Biophysics as the 'chicken and egg problem', who appeared first?

Thomas R. Cech and Albert Altmann discovered that certain types of RNA (Ribonucleic Acid) are capable of behaving both as nucleic acids and as enzymes (i.e. they are chicken and egg together) and called them "Ribozymes". At the suggestion of Walter Gilbert, the 'RNA world' was born at that time, i.e. it was thought that life had originated, in the primordial soup, through the spontaneous synthesis of a self-replicating RNA molecule and that this, as it evolved, learned to synthesise proteins.

The 'RNA world' also aroused great enthusiasm, but the major problems listed above were still passed over in silence.


 

 

RNA is a long chain of nucleotides consisting of the phosphate group, a sugar D-Ribose and one of four nitrogenous bases: Uracyl, Adenine, Cytosine, and Guanine. Ribose and nitrogenous bases have never been found in 'Miller's' experiments. Some experiments, which we can call 'non-Miller's' experiments carried out in the 1960s and 1970s have highlighted the possibility of the formation of Ribose together with other similar sugars and the formation of different nitrogenous bases.

1) Now, Ribose is a pentose (i.e. it contains 5 Carbon atoms) In pentoses, three carbon atoms are asymmetrical, and so there are three chiral centres. This means that the number of possible molecules (stereoisomers) is 23, i.e. 8, of which four are D (Destro) and four are L (Levo), including D Ribose. From an energy point of view in a prebiotic phase, they all have the same probability of being synthesised, so if D-Ribose has been formed, the others must also have been formed.

How was D Ribose separated from the other 7 pentoses?

2) In these experiments, several nitrogenous bases were obtained.

How were the four bases useful for RNA separated from all the others?

On the formation of these substances Christian De Duve in "Polvere vitale" 1995 writes: "[...] chemists have had some success in producing the five components of RNA, but with little success and under conditions at a time very different from a prebiotic scenario and different for each substance. If you want to combine the components in the right way, you run into other problems, of such magnitude, that no one has ever tried to do it in a prebiotic context.

3) In order to have a functional RNA, the bonds between these compounds to give origin to a nucleotide are not random but must occur at specific points of the molecules. We are not going to go into this aspect (already discussed in H1, "The RNA world in 2020") because upstream of all this is the fact that the formation of the nucleotide must take place with the elimination of water molecules and that this reaction in a primordial broth is chemically impossible.

 


How would nucleotides have formed in the primordial soup?

4) In the absence of O2, ribose and nitrogenous bases would have been destroyed by ultraviolet rays.

What could have done that?

There is not a single scientist who has tried to give an answer to these problems.

In conclusion, after about a decade and despite the contributions of many eminent researchers, the 'RNA world' proved to be another failure for the primordial soup theory.

And Christian De Duve in 'Polvere vitale' summarises: "It is honest to say that no mechanism has yet been found to satisfactorily explain prebiotic RNA synthesis, despite considerable efforts by some of the world's best chemists. Even the staunchest defenders of the RNA world have expressed pessimistic views on the future prospects of this line of research'.

And after a decade in 'Alle origini della vita' 2008 Christian De Duve adds: 'Despite all those efforts, attempts to reproduce RNA synthesis under prebiotic conditions have achieved only limited success. Researchers have assembled short RNA-like chains by means of mineral catalysts, mostly clays, with artificially activated nucleotides as precursors and a few selected moulds. However, the natural precursors have proved less effective, and their synthesis under plausible conditions has so far frustrated the researchers' ingenuity.

As a result of these difficulties, ad hoc solutions are being sought. Some scientists have already come up with one: before the "RNA World" perhaps there was a "pre-RNA World", which later gave rise to the "RNA World". Thus, instead of simplifying, the problem is complicated, much to Occam's chagrin.

Over the years, and up to the present day, the primordial soup has passed from a puddle to an ocean, then to a swamp to return, with the help of volcanoes, to an ocean, then back to a hot puddle undergoing evaporation to return again to an ocean but in the ocean floor near hydrothermal vents and finally to reservoirs for the 'RNA world'.

This constant search for ad hoc solutions only shows that at the beginning of the new millennium the primordial soup theory is still in deep crisis.

John Horgan in an article (Le Scienze, Quaderni n.89) writes: "None of these theories is credible enough to be considered as a paradigm, but none of them has been shown to be false, and this annoys Miller, who is known to be a rigorous experimentalist, but also a rather intransigent person".

Horgan continues: 'This approach, Miller protests, feeds the belief that the origin of life is of interest to a fringe of the scientific world, as a discipline unworthy of serious research.

From this statement we can deduce that there are no institutions that pay for serious and long-term research on the origin of life, and what is published is only the result of marginal, or to be more precise, 'idle' research.

And it is like saying that a theory is developed when a researcher, on the fringe of his field of research, discovers a clue that could be linked to the problem of the origin of life. And so astrophysicists think that life comes from space and find aliens on Earth. Geneticists take an 'RNA world' for granted, forgetting that it is only a hypothetical world. Metabolists give priority to the origin of proteins without even speculating on their physical origin. Of course, those who have discovered hydrothermal vents claim that life originated on the ocean floor. And all those who are baffled by the results of research and evolutionists prefer to speculate by dusting off the 'magic' word: chance.

And with regard to the theories on the origin of life, what Christian De Duve writes in 'Polvere vitale' is still valid today: 'What we have instead is a variety of theories, influenced by scientific specialisation, philosophical attitudes and the ideological leanings of their authors'.

In recent years, laboratory research has been greatly reduced, favouring research using computer models with obviously contradictory results.

In conclusion, experimental research has shown that life could not have originated in the prebiotic broth and therefore the prebiotic broth never existed. However, the metaphor of the primordial broth is so powerful that it has crystallised in the minds of scientists and, lazily, remains the most accepted theory.

 

                                                                                     Giovanni Occhipinti

 

Next article end of June.

The Prebiotic Broth (Part Two): Review of experiments and models from the last 12 years.

 


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